Epoxy resin compositions including novel phenol novolak condensates produced from bis(methoxymethyl)biphenyls

ABSTRACT

A bis(methoxymethyl)biphenyl having the formula (I): ##STR1## which is capable of producing by a dehalogenating coupling of a halogenated methoxymethylbenzene and which is useful as an intermediate for a phenol novolak condensate, an epoxy resin curing agent, an epoxy resin composition, or a phenol resin composition.

This application is a division of application Ser. No. 08/530,735, filedSep. 19, 1995, which application is entirely incorporated herein byreference now U.S. Pat. No. 5,612,442.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a bis(methoxymethyl)biphenyl useful asa starting material for a phenol novolak resin and an epoxy resinmodifier, any mixtures of six isomers thereof, and processes forproducing the same.

The present invention also relates to a novel phenol novolak condensateobtainable from a reaction between isomers of abis(methoxymethyl)biphenyl or a mixture thereof and a phenol compound.This condensate is useful as a curing agent for an epoxy resin and astarting material for an epoxidized novolak resin, in addition to beinguseful for a thermosetting resin with a cross-linking agent such ashexamethylenetetramine.

2. Description of the Related Art

As an aromatic bis(methoxymethyl) derivative, there has been known inthe past 1,4-bis(methoxymethyl)benzene. Phenol resins using this aredisclosed in Japanese Examined Patent Publication (Kokoku) No. 47-13782,Japanese Examined Patent Publication (Kokoku) No. 47-15111, and JapaneseExamined Patent Publication (Kokoku) No. 48-10960. However, abis(methoxymethyl)biphenyl has not been known. Japanese Examined PatentPublication (Kokoku) No. 47-13782 and Japanese Examined PatentPublication (Kokoku) No. 47-15111 disclose that a bis(alkoxymethyl)biphenyl can be used for the production of phenol polymers. However,there were no examples of experiments actually using it for a phenolpolymer.

Further, DE-2648701 discloses an example of the use of a 4,4'-isomer ofbis(methoxymethyl)biphenyl as a component of a flame retardentimprovement agent for polyvinyl chloride and an example of the synthesisof the same. According to this process, biphenyl is chloromethylated thebiphenyl, followed by reacting with methanol in the presence ofpotassium hydroxide, then synthesizing bis(methoxymethyl)biphenyl. Sincea 4,4'-isomer is produced at the chloromethylation stage, however, it isextremely difficult to synthesize a bis(methoxymethyl)biphenyl otherthan the 4,4'-isomer. Further, it is relatively easy to introduce asingle chloromethyl group into biphenyl, but introducing twochloromethyl groups is hard. According to this reference, the reactiontakes a long period of about 20 hours and further has a yield of about60%.

Accordingly, a process for the production of a novelbis(methoxymethyl)biphenyl other than the 4,4'-isomer, and anindustrially acceptable process for producing the same with a good yieldof bis(methoxymethyl)biphenyl, including the 4,4'-isomer, have beensought.

Phenol novolak resins have been used as materials for brake pads etc.mixed with asbestos fibers and other fibrous fillers due to their lowwearability, their good dimensional stability at high temperatures, andtheir good bonding ability, etc., but they have not necessarily beensatisfactory in terms of heat resistance, etc.

Further, novolak epoxy resins obtained from a reaction of epoxycompounds with the phenol novolak resins, in particular, cresol novolaktype epoxy resins, are inexpensive and are excellent in productivity,and therefore, these resins are widely used for semiconductor packages.These materials, however, sometimes have suffered from cracking, knownas the "popcorn phenomenon," which accompanies rapid vaporization andexpansion of the absorbed moisture at the time of solder reflow.Accordingly, a material having a low hygroscopicity and superior heatresistance has been sought. Improvement of the hygroscopicity and heatresistance is desired for the phenol novolak resins used as the curingagents of the epoxy resins as well.

As a method for solving the problem of heat resistance, it has beenproposed in Japanese Examined Patent Publication (Kokoku) No. 47-13782,Japanese Examined Patent Publication (Kokoku) No. 47-15111, and JapaneseExamined Patent Publication (Kokoku) No. 48-10960 to replace part or allof the formaldehyde with 1,4-bis(methoxymethyl)benzene or, in JapaneseUnexamined Patent Publication (Kokai) No. 4-110317, it is proposed thatbis(hydroxymethyl)benzene be reacted with a phenol compound to give aphenol polycondensate.

However, the epoxidated phenol resin obtained by this method isinsufficient in heat resistance and is insufficient in improvement ofhygroscopicity as well.

Further, a method for reducing the hygroscopicity property by anaddition reaction of divinylbenzene instead of formaldehyde, with thephenol, followed by reacting with the epoxy compound has been disclosedin Japanese Unexamined Patent Publication (Kokai) No. 5-78457, but theresult is not sufficient in terms of strength and low hygroscopicity.

Japanese Examined Patent Publication (Kokoku) No. 47-13782, JapaneseExamined Patent Publication (Kokoku) No. 47-15111, and JapaneseUnexamined Patent Publication (Kokai) No. 4-110317 disclose that it ispossible to use bis(methoxymethyl) biphenyl orbis(hydroxymethyl)biphenyl to obtain a phenol polycondensate, but thesepublications make no specific disclosure of the invention of thisapplication.

Further, Japanese Unexamined Patent Publication (Kokai) No. 5-117350discloses a specific example of a 2:1 condensate of 2 molecules ofphenol and 1 molecule of 4,4'-di(2-hydroxy-2-propyl)biphenyl. However,since this low molecular phenolic compound is crystalline and has a lowmelt viscosity, there is a problem that this compound is not easy tohandle due to its large flowability during molding. On the other hand,this reference discloses that it is possible to use4,4'-bis(methoxymethyl)biphenyl, but it does not specifically disclosethe invention of this application.

SUMMARY OF THE INVENTION

Accordingly, the objects of the present invention are to eliminate theabove-mentioned problems in the prior art and to provide a novelbis(methoxymethyl)biphenyl and a novel and effective production processthereof.

Other objects of the present invention are to provide novel phenolnovolak condensates and a new application for use thereof.

In accordance with the present invention, there is provided abis(methoxymethyl)biphenyl having the formula (I): ##STR2## providedthat the two CH₃ OCH₂ groups are not positioned at the 4,4'-positions.

In accordance with the present invention, there is also provided aprocess for producing a bis(methoxymethyl)biphenyl having the formula(I'): ##STR3## comprising effecting a dehalogenating coupling reactionof halogenated methoxymethylbenzene having the formula (II): ##STR4##wherein X is bromine, iodine or chlorine.

In accordance with the present invention, there is further provided aphenol novolak condensate obtainable from a reaction between an isomerof bis(methoxymethyl)phenyl having the above-defined formula (I') or amixture thereof and a phenol compound.

BRIEF DESCRIPTION OF THE DRAWING

The present invention will be better understood from the description setforth below with reference to the accompanying drawings.

FIG. 1 is a mass analysis chart in Example 1-6;

FIG. 2 is an infrared absorption spectrum in Example 1-6;

FIG. 3 is a result of ¹ H-NMR obtained in Example 1-6;

FIG. 4 is a mass analysis chart in Example 1-7;

FIG. 5 is an infrared absorption spectrum in Example 1-7;

FIG. 6 is a result of ¹ H-NMR obtained in Example 1-7;

FIG. 7 is a mass analysis chart in Example 1-8;

FIG. 8 is a result of ¹ H-NMR obtained in Example 1-8;

FIG. 9 is a GPC (i.e., gas permeation chromatography) chart of the resinobtained in Example 2-1;

FIG. 10 is a GPC chart of the resin obtained in Example 2-2;

FIG. 11 is a GPC chart of the resin obtained in Example 2-5; and

FIG. 12 is a GPC chart of the resin obtained in Example 2-6.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The inventors engaged in repeated intensive studies on a process ofproduction to obtain bis(methoxymethyl)biphenyl which is novel and forwhich there have been no effective means of synthesis and consequently,they discovered novel compounds serving as effective intermediates and,at the same time, established an economical, industrially practicalprocess of synthesis of the same and thereby completed the first andsecond aspects of the present invention.

According to the present invention a novel phenol novolak condensate andnew applications for use of the same are also provided. That is, theepoxy resin cured product obtained from a reaction of an epoxy resinwith the present condensate, as a curing agent, and the epoxy resincured product obtained from a reaction of an epoxy resin curing agentwith the epoxidized novolak resin obtained from the epoxidation of thepresent condensate exhibit extremely superior properties in terms ofhygroscopicity, heat resistance, and pliability. The novel phenolnovolak condensate according to the present invention and the epoxidizedresins obtained therefrom have advantageous characteristics such aspreferable molecular weight distribution and the small generation offlashes (or burrs) during the molding, and therefore, the productivitycan be improved. Further, the phenol resin cured product obtained bycuring the present condensate using hexamethylenetetramine or othercuring agents for phenol resins exhibits extremely superior properties,in terms of wear resistance, dimensional stability at high temperatures,and bonding properties.

As mentioned above, the bis(methoxymethyl)biphenyl according to thepresent invention has the above-specified formula (I), except4,4'-bis(methoxymethyl)biphenyl. The general formula (I') specificallyincludes the six types of bis(methoxymethyl)biphenyl of formulas (Ia) to(If). ##STR5##

Further, the present invention relates to a mixture containing isomersof the bis(methoxymethyl) biphenyl of the above general formula (I')wherein the total of the content of the 2,4'-isomer of the formula (Ic)and the content of the 4,4'-isomer of the formula (If) is at least 40%by weight. Preferably, it relates to a mixture wherein the content ofthe 2,4'-isomer is at least 40% by weight and the content of the4,4'-isomer is at least 40% by weight.

Further, the present invention relates to a process for producing thebis(methoxymethyl)biphenyl having the general formula (I') by effectinga dehalogenating coupling reaction of the halogenatedmethoxymethylbenzene having the general formula (II). The presentinvention in particular is a process suited to the production of the2,2'-isomer, 2,4'-isomer, or 4,4'-isomer and is suited to the productionof a mixture of a total content of the 2,4'-isomer and 4,4'-isomer of atleast 40% by weight or a mixture of a content of the 2,4'-isomer of atleast 40% by weight and a content of the 4,4'-isomer of at least 40% byweight. ##STR6## wherein, X is bromine, iodine, or chlorine.

The bis(methoxymethyl)biphenyl according to the present invention may besynthesized by the following process: ##STR7##

First, the process for synthesis of the intermediate halogenatedmethoxymethylbenzene will now be explained.

Process of Synthesis of methoxymethyliodobenzene (Step A of Process 1):

In the case of an iodide isomer, a mixture of the starting materialmethoxymethylbenzene, iodine, iodic acid, a catalyst, and a solvent isprepared by heating and stirring these components at a temperature of50° to 100° C. The amounts of the iodine and the iodic acid used are 1/4to 1/2 mole based upon 1 mole of the starting material. In particular,1/3 to 1/2.5 mole is suitable. If the amounts of these components aretoo small, 100% of the starting material is not consumed, while if theamounts are too large, unpreferable byproducts such as diiodide isomersetc., are produced.

The acid catalyst used in the above step is preferably a protonic acid.In particular, nonvolatile acids such as sulfuric acid and p-toluenesulfonic acid, are particularly preferred. The amount used is suitably1/5 to 1/30 mole, especially 1/2 to 1/15 mole, based upon 1 mole of thestarting material. If the amount of the acid catalyst is too small, thereaction rate becomes slow, while if it is too large, there is sometimesa problem with a rapid reaction occurring.

The solvent used in the present invention is a fatty acid type solventsuch as acetic acid or propionic acid. Acetic acid is particularlypreferred. The fatty acid type solvent may be used alone or in anymixture thereof, and it may be mixed with low boiling pointhydrocarbons, such as n-hexane and n-octane and halogenatedhydrocarbons, such as chloroform and dichloromethane.

The reaction is preferably carried out within a range of 40° to 120° C.,particularly suitably within a range of 60° to 90° C. If the temperatureis low, the reaction speed is slow, and when high, various byproductsare produced. The reaction time is preferably within a range of 3 to 12hours, particularly suitably within a range of 5 to 8 hours.

In this method for obtaining an iodide isomer, themethoxymethyliodobenzene which is normally obtained is a mixture of o-,m-, and p-isomers of the formulas (IIa) to (IIc). The proportions ofthese change according to the type of the halogen used and the reactionconditions, but normally a mixture of o-:m-:p-isomers of 1:(0.2 to0.4):(2 to 4) is obtained. ##STR8##

A specific isomer selected from the o-, m-, and p-isomers of themethoxymethyliodobenzene may be obtained by separation of the mixtureobtained by the above reaction by normal separation methods such asdistillation.

Method of Synthesis of Methoxymethylbromobenzene (Step A of Process 1):

A bromide isomer may be obtained by dropwise adding bromine to a mixtureof methoxymethylbenzene and a solvent such as dichloromethane at 0° to25° C. (see: e.g., Journal of the Chemical Society (JCS), 36, 1941)

Even in this method for obtaining a bromide isomer, themethoxymethylbromobenzene is normally obtained as a mixture of the o-,m-, and p-isomers of the formulas (IIa) to (IIc). The proportions of themixture will vary according to the type of the halogen used and thereaction conditions, but normally a mixture of o-:m-:p-isomers=1:(0.2 to0.4):(2 to 4) is obtained.

A specific isomer selected from the o-, m-, and p-isomers of themethoxymethylbromobenzene may be obtained by separation of the mixtureobtained by the above reaction by other normal separation methods suchas distillation.

Method of Synthesis of Methoxymethylchlorobenzene (Step C of Process 2):

A chloride isomer may be synthesized by reacting a p- or o-chlorobenzylchloride or mixtures thereof with NaOCH₃ in a solvent such as methanolat 40° to 90° C. to cause etherification.

Next, the synthesis of bis(methoxymethyl)biphenyl by a coupling reactionof halogenated methoxymethylbenzene will now be explained.

If a halogenated methoxymethylbenzene or a mixture of the three types ofisomers thereof are reacted in accordance with step B in the presence ofa nickel complex and a metal in a solvent, the dehalogenating couplingreaction occurs to thereby give bis(methoxymethyl) biphenyl.

The nickel complexes used herein are pyridine based complexes, such asbipyridyl nickel dichloride and bispyridine nickel dichloride, orphosphine based complexes, such as triphenylphosphine nickel dichloride,bisdiphenylphosphinoethane nickel dichloride, etc. Particularlypreferred are pyridine based complexes, especially bipyridyl nickeldichloride.

Here, the amount of the nickel complex used is 1/100 to 1 mole,preferably 1/15 to 1/50 mole, per mole of the halogenatedmethoxymethylbenzene. If the amount thereof is too small, the startingmaterial is not completely consumed, while if it is too large, there isthe problem of lack of economy.

As the metal, zinc, manganese, and magnesium may be used. These metalsare preferably used in the ordinary powder form. The amount used is 0.5to 2 moles, preferably 0.55 to 1 mole, per mole of the halogenatedmethoxymethylbenzene. If the amount thereof is too small, the startingmaterial is not consumed, while if it is too large, the reaction mixturebecomes slurry and is difficult to handle and, further, there is theproblem of a lack of economy.

The solvent used may be a solvent used for an ordinary coupling reactionas described in J. Org. Chem. 51, 2627 (1986); the Bull. Chem. Soc.Jpn., 63, 80 (1990), etc., that is, aprotonic polar solvents such asdimethylacetamide (DMAc) or dimethylformamide (DMF). However, in adehalogenating coupling reaction of a halogenated methoxymethylbenzene,a large amount of byproducts are produced, and in many cases, theprocess cannot be said to be industrially advantageous.

Thus, the present inventors engaged in detailed studies ondehalogenating coupling reactions and, as a result, found that theresults of the reaction differ tremendously depending upon thecombination of the type of the solvent and the metal used.

That is, if 1,3-dimethyl-2-imidazolidinone (DMI) and zinc powder, DMAcand manganese powder, DMF and manganese powder, and other combinationsare used, it is possible to obtain the desired isomers of thebis(methoxymethyl)biphenyl and their mixtures under moderate reactionconditions and at a high yield.

Further, it is preferable to perform the dehalogenating couplingreaction by heating a mixture of nickel complex and metal powder at atemperature of 100 -200° C. under a reduced pressure of 2 to 10 mmHg orunder a nitrogen atmosphere, then adding the halogenatedmethoxymethylbenzene and a solvent. In the various solvent-metal powdersystems, it is possible to obtain the desired product at a high yieldand, at the same time, the amounts of the catalyst, metal powder, andsolvent used can be reduced to 1/2 to 1/3 compared with the amounts usedshown in the above-mentioned J. Org. Chem., 51, (1986), 2627 etc.

As a result, an industrial and economical process for the production ofvarious types of bis(methoxymethyl) biphenyl isomers and their mixturesthrough a dehalogenating coupling reaction of a halogenatedmethoxymethylbenzene using a nickel-complex-metal powder catalyst systemcan be established.

This coupling reaction is suitably performed normally at a range of 50°to 200° C., particularly 70° to 180° C., for about 1 to 8 hours.

Further, the coupling may be performed by the following method:

First, as shown by step D, an ordinary method is followed to effect areaction between the halogenated methoxymethylbenzene and metalmagnesium or metal zinc to convert to a corresponding Grignard reagent.

Next, step E is followed to perform the dehalogenating coupling reactionin the presence of a metal complex of nickel, cobalt, etc.

The proportion of the six types of isomers obtained at this step is, inthe method using either of Zn or Mg, Ia:Ib:Ic:Id:Ie:If=1:(0.2 to 0.6):(4to 7):(0.01 to 0.1):(0.5 to 2.0):(5 to 15).

After the above coupling reaction, the inorganic substances are removedfrom the reaction solution, then distillation or recrystallationprocedures are used to obtain the bis(methoxymethyl)biphenyl. At thisstep, by performing precision distillation or careful recrystallization,it is possible to separate the solution into a number of componentswhereby mixtures of isomers in accordance with the present invention canbe obtained.

In the present invention, the proportions of production of the2,2'-isomer, 2,4'-isomer, and 4,4'-isomer are large, and therefore, thepresent invention is particularly suited to the production of theseisomers.

Further, to more efficiently produce specific isomers of thebis(methoxymethyl)biphenyl, it is particularly preferable to usespecific isomers as the starting materials used for the couplingreaction, that is, the halogenated methoxymethylbenzene. For example, toproduce 4,4'-bis(methoxymethyl)biphenyl, a p-methoxymethylhalobenzenecan be used as the starting material.

As mentioned above, the third embodiment of the present inventionrelates to a phenol novolak polycondensate obtained from a reactionbetween a phenol compound and the isomers of thebis(methoxymethyl)biphenyl of the above-specified formula (I) ormixtures thereof.

The phenol compound usable in the present invention means a compoundhaving at least one phenolic hydroxyl group at its aromatic ring.

Specific examples of such phenol compounds include unsubstituted phenolssuch as phenol, resorcinol, and hydroquinone; single substituted phenolssuch as cresol, ethylphenol, n-propylphenol, iso-propylphenol,t-butylphenol, octylphenol, nonylphenol, and phenylphenol; doublesubstituted phenols such as xylenol, methylpropylphenol,methylbutylphenol, methylhexylphenol, dipropylphenol, dibutylphenol,guaiacol, and catechol ethyl ether; triple substituted phenols such astrimethylphenol; naphthols such as naphthol, and methylnaphthol; andbisphenols such as bisphenol, bisphenol A, and bisphenol F.

The isomers of the bis(methoxymethyl)biphenyl having the formula (I)specifically are the compounds of the above-mentioned structuralformulas (Ia) to (If). These isomers may be used in any mixturesthereof.

Among these, the 2,4'-isomer shown by formula (Ic), the 4,4'-isomershown by formula (If), and a mixture of isomers containing at least 5%by weight of 2,4'-isomers and at least 40% by weight of 4,4'-isomers arepreferable. In particular, mixtures of isomers containing at least 5% byweight of 2,4'-isomer and at least 40% by weight of the 4,4'-isomer arepreferable. mixtures of isomers containing at least 10% by weight of2,4'-isomer and at least 40% by weight of 4,4'-isomer are the mostpreferable. Since the 2,4'-isomer is effective for increasing thebreakage energy of cured epoxy resins, a cured epoxy resin havingexcellent mechanical properties can be obtained when a phenol novolakcondensate obtained from a mixture containing 2,4'-isomer is used.

These bis(methoxymethyl)biphenyl isomers and mixtures thereof may beobtained by effecting a dehalogenating coupling reaction of ahalogenated methoxymethylbenzene. The proportion of the isomers in thereaction product generally is Ia:Ib:Ic:Id:Ie:If=(1):(0.2 to 0.6):(4 to7):(0.01 to 0.2):(0.5 to 2.0):(5 to 15), but it is possible to obtain aspecific isomer or a specific mixture of isomers by selecting thestarting materials and the reaction conditions.

Further, 4,4'-bis(methoxymethyl)biphenyl may be obtained bychloromethylating biphenyl, and then etherifying with sodium methoxide.

The phenol novolak condensate according to the present invention isobtained by effecting a reaction between isomers ofbis(methoxymethyl)biphenyl or mixtures thereof and a phenol compound inthe presence of an acid catalyst for 1 to 7 hours while demethanolating.

In this reaction, the proportion of the phenol compound and thebis(methoxymethyl)biphenyl mixture to be used is preferably within arange of 1:0.1 to 1. If the proportion is less than 0.1, a large amountof unreacted phenol has to be removed, whereby the process is madeuneconomical. Further, if the proportion is more than 1, gelation occurswhich is not desirable for a practical resin.

As the acid catalyst used in this reaction, p-toluenesulfonic acid,sulfuric acid, dimethylsulfuric acid, diethylsulfuric acid, etc. may bementioned. The amount used is preferably 1/10 to 1/100 mole per 1 moleof the phenol. If the amount is too small, the reaction rate becomesslow, while if it is too large, there is sometimes a problem with arapid reaction occurring and an inability to control the reaction.

The reaction temperature is preferably 120° to 190° C. If thetemperature is low, the reaction speed becomes slow, while if it ishigh, there is sometimes a problem such as gelation.

The phenol novolak condensate obtained in this way has the structure asshown in the general formula (III). Depending upon the type of thephenol compound used, there is a substituent on the phenol ring.##STR9##

Here, n differs according to the reaction conditions, but normally is aninteger of 0 to 9. When n=0, the molten viscosity is small, andtherefore, the compound easily flows during molding and is notpractical. Accordingly, for practical use, a mixture containing 50% byweight or more, preferably 60% by weight or more, of the condensatehaving n of 1 or more is preferable.

Next, the use of the phenol novolak condensate as a curing agent forepoxy resins will now be explained.

Since the phenol novolak condensate has a phenolic hydroxyl group, inthe same way as with normal phenol novolak resins, the phenol novolakcondensate can be used as a curing agent for epoxy resins. The curedproduct resulting from the use of this phenol novolak polycondensate asa curing agent is superior in hygroscopicity, heat resistance, andpliability.

Examples of the epoxy resin usable in this curing step are bisphenoldiglycydyl ether type epoxy resins which impart epoxy groups to abisphenol such as bisphenol A or bisphenol F; novolak type epoxy resinsimparting epoxy groups to a phenol novolak type resin such as normalphenol novolak resins, o-cresol novolak resins and brominated phenolnovolak resins; diphenylmethanediaminetrtraglycidyl ether,cyclohexanediaminetetraglycidyl ether, and other glycidylamine typeepoxy resins; polyethylene glycol diglycidyl ether, epoxidized SBR,epoxidized soybean oil, and other fatty acid epoxy resins;dihydroxybiphenyldiglycidyl ether type epoxy resins imparting epoxygroups to a dihydroxybiphenyl such as 4,4'-dihydroxybiphenyl,3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl;1,6-dihydroxynaphthalenediglycidyl ether and other condensationmulti-ring aromatic type epoxy resins. Among these, novolak type epoxyresins, dihydroxybiphenyldiglycidyl ether type epoxy resins andcondensation multi-ring aromatic type epoxy resins are preferred, and inparticular a novolak type epoxy resin is preferred.

To obtain an epoxy resin cured product using the phenol novolakcondensate of the present invention as a curing agent, the phenolnovolak condensate of the present invention and the above said epoxyresin are mixed so that the ratio of the hydroxyl groups of the phenolnovolak condensate of the present invention and the epoxy groups of theepoxy resin becomes generally equal and the resultant epoxy resincomposition is heated at about 100° to 250° C. In this reaction, it ispreferable to add to the epoxy resin composition a curing promotorgenerally used for promoting curing, for example, N-methylimidazole,triethylamine, triphenylphosphine, etc. Further, optionally or ifdesired, it is also possible to add a filler, coupling agent, flameretardant, lubricant, mold release agent, plasticizer, coloring agent,thickener, and other various types of additives.

Next, the application of the phenol novolak polycondensate as a startingmaterial for an epoxy resin will now be explained.

The phenol novolak condensate of the present invention may be made intoan epoxidized novolak resin by epoxidation. This epoxidized novolakresin, for example, includes a novolak type epoxy resin of the formula(IV) obtained by causing a reaction of the phenol novolak condensate ofthe present invention with epichlorohydrin or other epihalohydrins inthe presence of an alkali, ##STR10## wherein, n is an integer of from 0to 9. Further, there may be a substituent on the phenol ring dependingon the type of the phenol compound used as the starting material for thephenol novolak condensate.

The epoxidized novolak resin of the present invention may be cured withvarious types of curing agents. The cured product of the epoxy resin,like with the epoxy resin mentioned above, is superior inhygroscopicity, heat resistance, and pliability.

As the curing agent for an epoxy resin in this reaction, various typesof amines, polycarboxylic acids and their anhydrides, phenol novolakresins (including the phenol novolak polycondensate of the presentinvention), urea resins, melamine resins, etc. may be mentioned. Amongthese, ordinary phenol novolak resins, o-cresol novolak resins,brominated phenol novolak resins, and other phenol novolak resins,including the phenol novolak condensate of the present invention, arepreferred. Especially, the best results can be achieved when theepoxidized novolak resin of the present invention is cured with thephenol novolak condensate of the present invention as a curing agent.

To obtain the cured product of the epoxidized novolak resin of thepresent invention, it is possible, as with the curing method mentionedabove, to obtain the epoxy resin composition and then heat it. Further,there is the similarity that it is possible to add curing promoters andother additives.

Next, the use of the phenol novolak condensate of the present inventionas a starting material for a phenol resin (cured product) will beexplained.

To obtain a cured product of a phenol resin using the phenol novolakcondensate of the present invention, the phenol novolak condensate ofthe present invention and hexamethylenetetramine, formaldehyde, or othercuring agents for phenol resins are mixed to make the phenol resincomposition which is then heated at about 80 to 200° C., preferably 150°C. to 180° C. to cure it.

If desired, it is also possible to add, to the phenol resin compositionand phenol resin (cured product), a filler, coupling agent, flameretardant, lubricant, mold release agent, plasticizer, coloring agent,thickener, and other various types of additives. The phenol resin (curedproduct) thus obtained is superior in wear resistance, dimensionalstability at high temperatures, and bonding.

As explained above, the resin obtained by using the phenol novolakcondensate of the present invention as a curing agent for an epoxy resincan be used as an adhesive, paint, sealing material, friction material,grindstone, etc. and has superior properties in terms of heatresistance, closeness of adhesion, water absorption property, andmechanical properties.

Further, a resin obtained by curing the phenol novolak condensate usinghexamethylenetetramine or aldehydes may also be used as an adhesive,paint, sealing material, friction material, grindstone, etc. and hassuperior properties in terms of heat resistance, closeness of adhesion,water absorption property, and mechanical properties.

Further, a resin with superior properties is obtained even when addingto the phenol novolak resin and epoxidated novolak resin obtained in thepresent invention carbon black or other pigments, asbestos, silica,talc, and other fillers, glass fibers, rock wool, cotton, and otherreinforcing materials, etc.

EXAMPLES

The present invention will now be explained in more detail by, but by nomeans limited to, the following Examples.

Example 1-1 Iodination of Methoxymethylbenzene

Into a solution of 146.5 g (1.20 moles) of methoxymethylbenzene, 300 mlof acetic acid, and 80 ml of n-hexane 101.5 g (0.40 mole) of iodine,70.3 g (0.40 mole) of iodic acid, and 4 ml of sulfuric acid were added,then the mixture was stirred at 80° C. for 5 hours. 600 ml of n-hexaneand 700 ml of water were then added to the reaction solution, which wasthen shaken well, then the n-hexane layer was separated, washed, anddried. The solvent was distilled off, the solution was then distilledunder reduced pressure to obtain 216.5 g (0.87 mole) of a mixture of thethree types of isomers of methoxymethyliodobenzene.

Boiling point: 93° to 96° C./4 mmHg

Gas chromatography (column: Apiezon Grease L 10% on Uniport 2 m) gavetwo peaks (ratio of peak areas: 1:3). However, the results of ¹³ C-NMRmeasurement showed the presence of the m-isomer in addition to theo-isomer and the p-isomer. Based on these results, the isomers in thecomposition were found from ¹ H-NMR to beo-isomer:m-isomer:p-isomer=1:0.25:2.8.

Example 1-2 Bromination of Methoxymethylbenzene

Into a mixture of 12.2 g (0.1 mole) of methoxymethylbenzene, 8.2 g (0.1mole) of sodium acetate, and 100 ml of dichloromethane 12.0 g (75 mmole)of Br₂ was added dropwise over 3 hours at room temperature. Next, thesolution was raised to 60° C. and the reaction was continued for afurther 3 hours. After the end of the reaction, an aqueous solution ofsodium sulfite was added to deactivate the remaining bromine, then thedichloromethane layer was separated by a liquid separation procedure.This was washed with water and dried, then analyzed by gaschromatography, whereby it was found that 18.3 g (91 mmole) of a mixtureof three types of isomers of methoxymethylbromobenzene was obtained. Theproportions of the isomers in the composition were

o-isomer:m-isomer:p-isomer=1:0.20:3.8

Example 1-3 Deiodo-coupling of Methoxymethyliodobenzene

A mixture comprised of 174.3 g (0.70 mole) of themethoxymethyliodobenzene obtained in Example 1-1 (mixture of three typesof isomers), 14.2 g (46.7 mmole) of bipyridyl nickel dichloride(Ni(bipy)Cl₂.H₂ O), 50.4 g (0.77 g atom) of zinc powder, 9.2 g (0.117mole) of pyridine, and 350 ml of DMI was stirred vigorously at 90° C.for 5.5 hours. After the end of the reaction, the solids were removed bysuction filtration and the majority of the solvent was removed bydistillation under reduced pressure. The residue was cooled, then a 5%aqueous solution of hydrochloric acid was added to the residue, whichwas then sufficiently mixed and separated. The oily layer portion wasfurther washed with water and the remaining small amount of solvent wasdistilled off under reduced pressure. The residue was analyzed by gaschromatography (SE-30, 5%, 2 m, 120° to 230° C.), as a result of whichit was found that 80.3 g (0.332 mole) of a mixture of six isomers ofbis(methoxymethyl)biphenyl was obtained.

The proportions of the isomers were2,2'-:2,3'-:2,4'-:3,3'-:3,4'-:4,4'=1:0.5:5.5:0.08:0.3:7.5

Example 1-4 Debromo-coupling of Methoxymethylbromobenzene

20.1 g (0.10 mole) of the methoxymethyl-bromobenzene mixture obtained inExample 1-2, 2.04 g (6.7 mmole) of Ni(bipy)Cl₂.H₂ O, 7.19 g (0.11 gatom) of zinc powder, 1.32 g (16.7 mmole) of pyridine, and 50 ml of DMIwere stirred vigorously at 90° C. for 5.5 hours. After the end of thereaction, the same post-treatment and analysis were performed as inExample 1-3, whereby 11.5 g (47.5 mmole) of a mixture of six isomers ofbis(methoxymethyl)biphenyl was obtained.

The proportions of the isomers were

2,2'-:2,3'-:2,4'-:3,3'-:3,4'-:4,4'-=1:0.4:7.6:0.04:1.3:14.2

Example 1-5 Dechloro-coupling of Methoxymethylchlorobenzene

30.4 g (0.1 mole) of Ni(bipy)Cl₂.H₂ O and 90.5 g (1.65 g atom) ofmanganese powder were taken up in a 3-liter four-necked flask equippedwith a cooling tube, gas introduction tube, and stirring device. Thiswas heated at 100° C. for 1 hour under the flow of nitrogen gas.

Next, a mixture of 352.1 g (2.25 mole) of p-methoxymethylchlorobenzene,117.4 g (0.75 mole) of o-methoxymethylchlorobenzene, and 1.5 liters ofDMAc was added to the above four-necked flask. The mixture was thenvigorously stirred at 120° C. to cause a reaction for 3 hours.

The solution was cooled to room temperature, then the solids werefiltered out and the filtrate was distilled under reduced pressure tothereby distill off the DMAc. 400 ml of a 3 percent aqueous solution ofhydrochloric acid was added to the residue, the mixture was sufficientlystirred, then the precipitate was filtered out. The filtrate wassuccessively washed by 250 ml of 3% aqueous solution of sodium carbonateand 250 ml of water and the oily layer portion was distilled underreduced pressure at 200° C. and 3 Torr to obtain 328.4 g (1.36 mole) ofthe 154° to 174° C. fraction. This liquid was measured by gaschromatography, whereupon it was found that the purity was 99.6% and theyield of the desired substance was 90.0%.

The proportions of the isomers were

2,2'-:2,4'-:4,4'-=0.2:42.6:55.8

Example 1-6 Synthesis of 2,2'-bis(methoxymethyl)biphenyl byDechloro-coupling of o-Methoxymethylchlorobenzene

10.03 g (33 mmole) of Ni(bipy)Cl₂.H₂ O and 30.1 g (0.55 g atom) ofmanganese powder were taken up in a 300-ml four-necked flask equippedwith a cooling tube, gas introduction tube, and stirring device. Thiswas heated at 120° C. for 1 hour under the flow of nitrogen gas.

Next, a mixture of 156.6 g (1.00 mole) of o-methoxymethylchlorobenzeneand 300 ml of DMAc was added to the above four-necked flask. The mixturewas then vigorously stirred at 120° C. to cause a reaction for 5 hours.

The solution was cooled to room temperature, then the solids werefiltered out and the filtrate was distilled under reduced pressure tothereby distill off the DMAc. 100 ml of toluene and 130 ml of a 3%aqueous solution of hydrochloric acid was added to the residue, themixture was sufficiently stirred, then the precipitate was filtered out.The precipitate was washed with 100 ml of toluene, the filtrate and thewashings were combined, and successive washing was performed by 130 mlof 3% aqueous solution of sodium carbonate and 200 ml of water. Thetoluene layer was distilled under reduced pressure to obtain a residuewhich was recrystallized by n-hexane to obtain 105.4 g (0.435 mole) of2,2'-bis(methoxymethyl)biphenyl as a white solid. The purity was 99.5%and the yield of the desired substance was 86.5%.

The results of element analysis were

H:C=7.58:79.06

The mass analysis (EI) was as shown in FIG. 1.

The infrared absorption spectrum was as shown in FIG. 2.

The results of the ¹ H-NMR (solvent: CDCl₃) were as shown in FIG. 3.

Example 1-7 Synthesis of 4,4'-bis(methoxymethyl)biphenyl byDechloro-coupling of p-Methoxymethylchlorobenzene

1.43 g (5 mmole) of Ni(bipy)Cl₂.H₂ O and 4.62 g (0.0824 g atom) ofmanganese powder were taken up in a 100-ml four-necked flask equippedwith a cooling tube, gas introduction tube, and stirring device. Thiswas heated at 100° C. for 1 hour under a reduced pressure of 5 Torr.

Next, the mixture was cooled to room temperature, then a mixture of23.49 g (150 mmoles) of p-methoxymethylchlorobenzene and 52 ml of DMAcwas added to the above four-necked flask. The mixture was thenvigorously stirred at 120° C. to cause a reaction for 3 hours.

The solution was cooled to room temperature, then the solids werefiltered out, and the filtrate was distilled under reduced pressure tothereby distill off the DMAc. 20 ml of a 3% aqueous solution ofhydrochloric acid was added to the residue, the mixture was sufficientlystirred, then the precipitate was filtered out. The filtrate wassuccessively washed by 20 ml of 3% aqueous solution of sodium carbonateand 20 ml of water. The oily layer portion was subjected to evaporationunder reduced pressure at 200° C. and 3 Torr to obtain 17.82 g (73.6mmole) of the fraction at 170° to 174° C., whereby4,4'-bis(methoxymethyl)biphenyl was obtained. This was a solid at roomtemperature. Analysis by gas chromatography showed its purity was 98.7%.The yield of the desired substance was 96.8%.

The results of element analysis were

H:C=7.52:79.34

The mass analysis (EI) was as shown in FIG. 4.

The infrared absorption spectrum was as shown in FIG. 5.

The results of the ¹ H-NMR (solvent: CDCl₃) were as shown in FIG. 6.

Example 1-8 Synthesis of 2,4'-bis(methoxymethyl)biphenyl

When a mixture of the bis(methoxymethyl)biphenyl isomers obtained inExample 1-5 was cooled to 0° C., the 4,4'-isomer precipitates, so byquick filtering, a filtrate containing about 75% 2,4'-isomer wasobtained.

This filtrate was distilled under reduced pressure at 180° C. and 3.5Torr and the fraction at 155° C. was taken to obtain the2,4'-bis(methoxymethyl)biphenyl. The purity was 92%.

The results of the ¹ H-NMR (solvent: CDCl₃) were as shown in FIG. 7. Itwas learned that there were eight types of the H of the benzene ring.

The infrared absorption spectrum was as shown in FIG. 8.

The bis(methoxymethyl)biphenyl of the present invention can be used forthe applications explained below.

The bis(methoxymethyl)biphenyl or the bis(methoxymethyl)biphenylmixtures of the present invention may be allowed to react with phenolcompounds to produce phenol novolak condensates.

These phenol novolak condensates may be used as epoxy resin curingagents or these phenol novolak condensates may be epoxidized to formepoxidized novolak resins.

Example 2-1 Synthesis of Phenol Novolak Condensate (Resin A)

564 g (6 moles) of phenol and 484 g (2 mole) of the mixture of generalformula (I') (Ia:Ib:Ic:Id:Ie:If=1:0.2:6:0.01:0.5:8.5) were charged intoa flask provided with a stirrer and a cooler, then 15.4 g (0.1 mole) ofdiethyl sulfate was added dropwise. The reaction was continued for 3hours while holding the reaction temperature at 160° C. During thistime, the alcohol produced was removed by distillation.

After the reaction ended, the mixture was cooled, then washed with waterthree times. The oil layer was separated and the unreacted phenol wasremoved by distillation under reduced pressure to obtain 700 g of theresin (A). The softening point of the obtained resin (A) was 74° C. andthe hydroxyl equivalent was 175 g/eq. The GPC (i.e., gel permeationchromatography) data of the resultant resin was shown in FIG. 9, whichshowed that the weight ratio of the condensates having n of 1 or morewas 63.8% and the weight average of n was 0.6.

Example 2-2 Synthesis of Phenol Novolak Condensate (Resin B)

The same reaction was performed as in Example 2-1 except that 470 g ofphenol was used to obtain 720 g of the resin (B). The softening point ofthe resin was 78° C. and the hydroxyl equivalent was 175 g/eq.

The GPC data of the resultant resin was shown in FIG. 10, which showedthat the weight ratio of the condensates having n of 1 or more was 71.0%and the weight average of n was 0.9.

Example 2-3 Synthesis of Epoxidated Novolak Resin (Resin C)

175 g of the resin (A) obtained in Example 2-1, 555 g (6 mole) ofepichlorohydrin, and 50 g of methanol were mixed and dissolved together.While holding the reaction temperature at 50° C., 40 g (1 mole) of solidNaOH was added bit by bit. After the end of the addition, the reactionwas continued for 2 hours. The temperature was raised to 70° C., thenthe reaction was continued for two further hours.

After the end of the reaction, the byproduct salt was removed by washingwith water, then the unreacted epichlorohydrin was removed bydistillation under reduced pressure. 400 g of methylisobutylketone wasadded to the residue to make a uniform solution, then 20 g of a 20%aqueous solution of NaOH was added to the mixture, the temperature wasraised to 70° C., and a reaction was caused for 1 hour.

After the end of the reaction, the mixture was washed with water a totalof 5 times until the washings became neutral. The organic layer wasseparated and the methylisobutylketone was distilled off so as to obtain228 g of the epoxy resin (C). The softening point of this resin was 60°C. and the epoxy equivalent was 239 g/eq.

Example 2-4 Synthesis of Epoxidated Novolak Resin (Resin D)

The same reaction was performed as in Example 2-3 except that 175 g ofthe resin (B) was used to obtain 225 g of the epoxy resin (D). Thesoftening point of the resin was 64° C. and the epoxy equivalent was 239g/eq.

Example 2-5 Synthesis of Phenol Novolak Condensate (Resin E)

The same procedure was performed as in Example 2-1 using 117.5 g (1.25mole) of phenol and 121.0 g (0.50 mole) of4,4'-bis(methoxymethyl)biphenyl and adding dropwise 0.11 ml of 48%sulfuric acid instead of diethyl sulfate. The reaction was caused for 3hours holding the reaction temperature at 150° C. to obtain 158 g of theresin (E).

The softening point of the resultant resin (E) was 82.6° C. and thehydroxyl equivalent was 199 g/eq.

The GPC data of the resultant resin was shown in FIG. 11, which showedthat the weight ratio of the condensates having n of 1 or more was64.9%.

Example 2-6 Synthesis of Phenol Novolak Polycondensate (Resin F)

The same reaction was performed as in Example 2-5 except that a mixtureof bis(methoxymethyl)biphenyl of 50% 2,4'-isomers and 50% 4,4'-isomerswas used to obtain 156 g of the resin F.

The softening point of the resultant resin (F) was 82.0° C. and thehydroxyl equivalent was 199 g/eq.

The GPC data of the resultant resin was shown in FIG. 12, which showedthat the weight ratio of the condensate having n of 1 or more was 68.5%and the weight average of n was 0.8.

The proportions of the formulations of the epoxy resin composition whenusing the resins (A), (B), (E), and (F) obtained in the above Examplesas curing agents for epoxy resins, the properties of those curedproducts, the proportions of formulations of the epoxy resincompositions comprised of the resins (C) and (D) the epoxy curingagents, the properties of these cured products and, also, theproportions of the formulations of the epoxy resin composition comprisedof the resin (C) as an epoxy resin and the resin (A) as a curing agentare shown in Table 1 and Table 2.

The phenol novolak resin in Tables 1 and 2 was the H-1 made by MeiwaKasei K.K. (softening point 86° C., hydroxyl equivalent 104 g/eq), whilethe epoxidized-o-cresol novolak resin was the EOCN-1020 made by NihonKayaku K.K. (softening point 70° C., epoxy equivalent 200 g/eq). Silicaused as a filler was RD-8 made by Tatumori Kagaku K.K. andtriphenylphosphine was used as a curing accelerator.

Preparation of Test Pieces and Test Methods for Measurement of PhysicalProperties Shown in Table 1

The components shown in Table 1 were blended, then were heated to 150°C. to melt and mix. The mixture was deaerated by vacuum, then pouredinto a mold (thickness 4 mm) of 150° C. and allowed to cure (cured at150° C. for 3 hours, then cured at 180° C. for 5 hours).

Test Methods

Water absorption rate: Dimensions of test pieces 25×70×4 mm, 24 hours,boiling method

Breakage energy, flexural modulus, flexural strength: 3-point bendingmethod, dimensions of test piece 4×6×70 mm

Tg: TMA (Thermal Mechanical Analysis) method

Preparation of Test Pieces and Test Method for Measurement of PhysicalProperty Shown in Table 2

The adhesive of Table 2 was blended and melted at 150° C., then themelted adhesive was coated on 10 mm of one end of prestripped coatingpieces (aluminum foil of 0.1×20×100 mm). The coating pieces were stackedto adjust to a thickness of the adhesive of 0.1 mm, then were clamped inplace and cured (cured at 150° C. for 3 hours, then cured at 180° C. for5 hours). After curing, the T-type peel strength (bonding strength) wasmeasured.

From the results of Table 1 and Table 2, it is understood that thephenol novolak condensate and epoxidized phenol resin using the compoundof the formula (I) exhibited superior values in all properties, such aswater absorption, mechanical properties, and bonding property comparedwith conventional products.

Further, the generation of flashes was not observed.

Examples of the formulations of the phenol resin compositions using theresin (A) and (B) obtained in Examples 2-1 and 2-2 and the properties ofthe cured products of the composition are shown in Table 3. The testspecimens for the determination of various physical properties shown inTable 3 were prepared and the tests were carried out as follows.

The components shown in the formulation of Table 3 were mixed. Aftermixing, the mixture was placed in a mold for flexural strength test(size 10×10×100 mm) and molded and cured under a molding pressure of 200kg/cm² at 160° C. for 5 minutes. After curing, the test specimens wereheated at 250° C., 260° C. or 270° C. for 500 hours as a test for heatresistance thereof and, after cooling, the flexural strength wasdetermined at an ordinary temperature.

As is clear from the results shown in Table 3, the phenol novolak resinsobtained from the use of the compound (I') exhibit excellent values inthe heat resistance and mechanical characteristics, compared with theconventional product.

                                      TABLE 1                                     __________________________________________________________________________                   Composition                                                                   Ex. 1                                                                             Ex. 2                                                                             Ex. 3                                                                             Ex. 4                                                                             Comp. Ex. 1                                                                         Ex. 5                                                                             Ex. 6                                                                             Ex. 7                            __________________________________________________________________________    Composition                                                                   Resin (A) (parts)                                                                            91.5                                                                              --  --  --  --    --  --  73                               Resin (B) (parts)                                                                            --  91.5                                                                              --  --  --    --  --  --                               Resin (C) (parts)                                                                            --  --  100 --  --    --  --  100                              Resin (D) (parts)                                                                            --  --  --  100 --    --  --  --                               Resin (E) (parts)                                                                            --  --  --  --  --    99  --  --                               Resin (F) (parts)                                                                            --  --  --  --  --    --  99  --                               Phenol novolak resin (parts)                                                                 --  --  44  44  52    --  --  --                               Epoxidated o-cresol novolak resin                                                            100 100 --  --  100   100 100 --                               (parts)                                                                       Triphenylphosphine (parts)                                                                   0.24                                                                              0.24                                                                              0.24                                                                              0.24                                                                              0.24  0.275                                                                             0.31                                                                              0.24                             __________________________________________________________________________                   Cured 1                                                                           Cured 2                                                                           Cured 3                                                                           Cured 4                                                                           Comp. Ex.                                                                           Cured 5                                                                           Cured 6                                                                           Cured 7                          __________________________________________________________________________    Physical properties                                                           Water absorption (%)                                                                         0.83                                                                              0.78                                                                              0.71                                                                              0.72                                                                              1.10  0.81                                                                              0.80                                                                              0.65                             Breakage energy (kgf/mm)                                                                     75.16                                                                             74.82                                                                             79.32                                                                             80.57                                                                             56.31 74.30                                                                             78.51                                                                             82.56                            Flexural modulus (kgf/mm.sup.2)                                                              359.23                                                                            362.23                                                                            358.91                                                                            360.22                                                                            335.51                                                                              365.8                                                                             378.2                                                                             361.50                           Flexural strength (kgf/mm.sup.2)                                                             15.46                                                                             16.31                                                                             16.42                                                                             16.22                                                                             14.96 15.20                                                                             16.60                                                                             17.02                            Tg (° C.)                                                                             137 139 140 138 134   140 138 139                              __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________                   Composition                                                                   Ex. 1                                                                             Ex. 2                                                                             Ex. 3                                                                             Ex. 4                                                                             Comp. Ex. 1                                                                         Ex. 5                                                                             Ex. 6                                                                             Ex. 7                            __________________________________________________________________________    Composition                                                                   Resin (A) (parts)                                                                            91.5                                                                              --  --  --  --    --  --  73                               Resin (B) (parts)                                                                            --  91.5                                                                              --  --  --    --  --  --                               Resin (C) (parts)                                                                            --  --  100 --  --    --  --  100                              Resin (D) (parts)                                                                            --  --  --  100 --    --  --  --                               Resin (E) (parts)                                                                            --  --  --  --  --    99  --  --                               Resin (F) (parts)                                                                            --  --  --  --  --    --  99  --                               Phenol novolak resin (parts)                                                                 --  --  44  44  52    --  --  --                               Epoxidated o-cresol novolak resin                                                            100 100 --  --  100   100 100 --                               (parts)                                                                       Triphenylphosphine (parts)                                                                   0.24                                                                              0.24                                                                              0.24                                                                              0.24                                                                              0.24  0.275                                                                             0.31                                                                              0.24                             Silica (parts) 191.74                                                                            191.74                                                                            144.24                                                                            144.24                                                                            152.24                                                                              199.28                                                                            199.31                                                                            173.24                           __________________________________________________________________________                   Cured 1                                                                           Cured 2                                                                           Cured 3                                                                           Cured 4                                                                           Comp. Ex.                                                                           Cured 5                                                                           Cured 6                                                                           Cured 7                          __________________________________________________________________________    Bonding strength (g/cm)                                                                      960 813 1015                                                                              1020                                                                              50    960 950 1110                             __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________                                       Comparative                                                     Composition 8                                                                        Composition 9                                                                        Example                                    __________________________________________________________________________    Formulation (wt. parts)                                                       Resin (A)            100    --     --                                         Resin (B)            --     100    --                                         Phenol Novolak Resin.sup.*1                                                                        --     --     100                                        Hexamethylenetetramine                                                                             17     17     17                                         Glass fiber.sup.*2   70     70     70                                         Physical Properties                                                           Flexural strength (kgf/mm.sup.2)                                                          (250° C. × 500 hr)                                                        20.6   21.3   5.8                                        "           (260° C. × 500 hr)                                                        19.6   19.8   4.7                                        "           (270° C. × 500 hr)                                                        19.1   18.7   3.5                                        __________________________________________________________________________     .sup.*1 Conventional resin (phenol novolak resin H1, s.p. = 86° C.     available from Meiwa Kasei K.K.)                                              .sup.*2 Chopped strand (5 mm) available from Nittobo K.K.                

According to the present invention, it is possible to industrially andeconomically produce various types of bis(methoxymethyl)biphenyl isomersand mixtures thereof using a nickel complex-metal powder catalyst systemand through a dehalogenating coupling reaction of a halogenatedmethoxymethylbenzene. It is possible to economically provide a novelbis(methoxymethyl)biphenyl which is a useful intermediate, but for whichthere has been no effective means of synthesis.

Further, the present invention provides a novel phenol novolakcondensate which can be used for a thermosetting resin, a curing agentof an epoxy resin, the starting material of an epoxidized novolak resin,etc. The phenol novolak condensate and epoxidized phenol resin of thepresent invention are superior to conventional products in the waterabsorption property, mechanical properties, bonding properties, etc.Furthermore, bis(methoxymethyl)biphenyl is produced in the reaction atthe time of production. There is no particular need for refinement. Thereaction is a demethanolation reaction as opposed to the prior art,which was a dehydration reaction, and therefore is also advantageoustechnically and economically.

We claim:
 1. An epoxy resin composition comprising a phenol novolakcondensate obtained from a reaction between (a) a mixture of isomers ofa bis(methoxymethyl)biphenyl having the formula (I') including at least40% by weight of a mixture of a 2,4'-isomer ofbis(methoxymethyl)biphenyl and a 4,4'-isomer ofbis(methoxymethyl)biphenyl, wherein the mixture of isomers includes atleast 5% by weight of a 2,4'-isomer of bis(methoxymethyl)biphenyl, and(b) a phenol compound, wherein formula (I') is as follows: ##STR11## anepoxy resin.
 2. An epoxy resin composition according to claim 1, whereinthe mixture of isomers includes at least 40% by weight of a 2,4'-isomerof bis(methoxymethyl)biphenyl.
 3. An epoxy resin composition accordingto claim 1, wherein the mixture of isomers includes at least 10% byweight of a 2,4'-isomer of bis(methoxymethyl)biphenyl.
 4. An epoxidizednovolak resin obtained by epoxidizing a phenol novolak condensateobtained from a reaction between (a) a mixture of isomers of abis(methoxymethyl)biphenyl having the formula (I') including at least40% by weight of a mixture of a 2,4'-isomer ofbis(methoxymethyl)biphenyl and a 4,4'-isomer ofbis(methoxymethyl)biphenyl, wherein the mixture of isomers includes atleast 5% by weight of a 2,4'-isomer of bis(methoxymethyl)biphenyl, and(b) a phenol compound, wherein formula (I') is as follows: ##STR12## .5. An epoxy resin composition comprising an epoxidized novolak resinobtained by epoxidizing a phenol novolak condensate obtained from areaction between (a) a mixture of isomers of abis(methoxymethyl)biphenyl having the formula (I') including at least40% by weight of a mixture of a 2,4'-isomer ofbis(methoxymethyl)biphenyl and a 4,4'-isomer ofbis(methoxymethyl)biphenyl, wherein the mixture of isomers includes atleast 5% by weight of a 2,4'-isomer of bis(methoxymethyl)biphenyl, and(b) a phenol compound, wherein formula (I') is as follows: ##STR13## acuring agent for an epoxy resin.
 6. An epoxy resin compositioncomprising an epoxidized novolak resin obtained by epoxidizing a phenolnovolak condensate obtained from a reaction between (a) a mixture ofisomers of a bis(methoxymethyl)biphenyl having the formula (I')including at least 40% by weight of a mixture of a 2,4'-isomer ofbis(methoxymethyl)biphenyl and a 4,4'-isomer ofbis(methoxymethyl)biphenyl, wherein the mixture of isomers includes atleast 5% by weight of a 2,4'-isomer of bis(methoxymethyl)biphenyl, and(b) a phenol compound, wherein formula (I') is as follows: ##STR14## thephenol novolak condensate obtained from a reaction between (a) a mixtureof isomers of a bis(methoxymethyl)biphenyl having the formula (I') and(b) a phenol compound, as a curing agent for an epoxy resin.
 7. An epoxyresin composition according to any one of claims 1 and 4-6, wherein thephenol compound includes a member selected from the group consisting of:phenol, resorcinol, hydroquinone, cresol, ethylphenol, n-propylphenol,iso-propylphenol, t-butylphenol, octylphenol, nonylphenol, phenylphenol,xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol,dipropylphenol, dibutylphenol, guaiacol, catechol ethyl ether,trimethylphenol, naphthol, methylnaphthol, bisphenol A, and bisphenol F.